High molecular weight nitrogen-containing condensates and fuels and lubricants containing same

ABSTRACT

Improved additives/detergents for lubricant and fuel compositions are obtained by condensing a hydroxyalkyl or hydroxyaryl compound with an amine compound. The condensates according to the present invention are produced by the acid catalyzed condensation of the amine reactant with the hydroxy reactant.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of co-pending U.S. Ser. No. 07/936,700filed on Aug. 27, 1992, now U.S. Pat. No. 5,230,719, which is adivisional of U.S. Ser. No. 07/714,579 filed on Jun. 13, 1991, now U.S.Pat. No. 5,160,648, which is a divisional of U.S. Ser. No. -7/390,439filed on Aug. 3, 1988, now U.S. Pat. No. 5,053,152, which is acontinuation of U.S. Ser. No. 06/711,799 filed on Mar. 14, 1985,abandoned.

BACKGROUND

1. Field of the Invention

This invention relates to a high molecular weight N-containingcondensate useful in lubricant and fuel compositions. More specifically,this invention relates to an additive and a dispersing aid forlubricants and fuel compositions, including dispersants that exhibit ahigh total base number and contain a low free amine content. Thecondensates of the present invention are produced by the acid catalyzedcondensation of an amine reactant with a hydroxy alkyl or hydroxy arylreactant.

2. State of the Art

Nitrogen containing dispersing aids for lubricants and fuel compositionsare known and widely used in this technology. For example, in U.S. Pat.Nos. 3,219,666 and 3,272,746 various nitrogen containing "ashless" typedispersing agents for lubricants and fuel compositions are disclosed.

In U.S. Pat. No. 4,428,849 an alkenyl succinimide or borated alkenylsuccinimide is reacted with an alkylene polyamine to produce adispersant for lubricant oil useful for diesel engines.

U.S. Pat. No. 4,234,435, discloses various carboxylic acid acylatingagents which can be further reacted with such reactants as polyethylenepolyamines and polyols to produce derivatives useful as lubricantadditives or as intermediates for further post treatment which findother uses in the lubricant additive technology.

U.S. Pat. No. 4,477,362 discloses various nitrogen- and oxygen-containing compositions which are prepared by reacting an aliphatichydroxy compound with at least one tertiary amino alkanol to producederivatives useful as lubricant and fuel additives.

U.S. Pat. No. 4,200,545 describes various amino phenols which may becombined with a hydrocarbyl amine or acylated nitrogen containingcompound which resultant composition finds use as additives for fuelsand lubricants to be added to 2-cycle engines.

U.S. Pat. No. 4,116,643 discloses amine salts of carboxylate half esterswhich are the reaction products of organic acid materials and hydroxyamines which materials find use as anti-rust additives for hydrocarbonfuels, such as gasoline and middle distillates.

None of the above-discussed patents disclose nor suggest the highmolecular weight nitrogen-containing condensates of the presentinvention, i.e., condensing a high molecular weight polyamine reactantwith a hydroxy alkyl or hydroxy aryl reactant.

SUMMARY OF THE INVENTION

In accordance with the present invention, a novel, high molecular weightextended polyamine has been discovered which has a viscosity greaterthan the viscosity of the amine reactant. The viscosity of the polyaminecondensate, according to the present invention, may range up to theproduction of solid material depending upon the reaction conditions andthe desired properties of the final product.

Further, in accordance with the invention, it has been found that theextended polyamines of the present invention are useful in thepreparation of dispersants having substantially no free amine andimprove the performance of lubricant and fuel compositions.

Still further, in accordance with the invention, it has been found thatpolyamines of the present invention may be used alone as dispersants andadditives for lubricant and fuel compositions or may be further reactedwith, for example, an acylating agent, to give an even higher molecularweight dispersant.

Still further, in accordance with the invention, a high yield, singlestep reaction comprising the dehydration condensation of at least onepolyamine reactant with at least one hydroxy alkyl or hydroxy arylreactant in the presence of an acid catalyst has been developed for thepreparation of the high molecular polyamines of the present invention.

Still further, in accordance with the invention, various lubricantcompositions, fuel compositions and other such functional fluidcompositions comprising the high molecular weight extended polyamines orthe reaction products thereof according to the present invention arecontemplated and within the scope of the invention.

These and other aspects of the invention will become clear to thoseskilled in the art upon the reading and understanding of thespecification.

DETAILED DESCRIPTION OF THE INVENTION

A novel class of high molecular weight polyamines has surprisingly beendiscovered and are illustrated by the following formula: ##STR1##wherein R is independently hydrogen or hydrocarbyl, R' is hydrogen,alkyl or NH₂ R"[NR"]_(y) wherein y ranges from 1 to about 6 and R" is analkylene group of 1 to about 10 carbon atoms, X is an alkylene group ofat least 1 carbon atom, Y represents sulfur, nitrogen, or oxygen, A ishydrocarbyl, Z is alkylene of 1 to about 10 carbon atoms, oxyalkylene of1 to about 10 carbon atoms or a heterocyclic ring containing at leastone nitrogen atom, and wherein n is 0 or 1 dependent upon m and q, q if0 or 1, m is 1, 2 or 3, x is 1 to about 10 and u is a whole integergreater than one.

In a preferred embodiment, X and A combined must consist of at least 2carbon atoms. In one embodiment, the polyamine units according to theabove formula (I) may be defined by the formula: ##STR2## wherein R, R',A, Z, x and u are the same defined in formula (I) and e is 1 or 2.

The above described polyamines, as illustrated by Formula (I), arederived from:

(A) an hydroxy alkyl or hydroxy aryl reactant represented by formula(II) below: ##STR3## wherein R, Y, Z, A, n, q and m are the same asdefined hereinabove, and

(B) a polyamine reactant illustrated by the formula (III) below:##STR4## wherein R, R', Z and x are the same as defined hereinabove.

As used herein, the term "hydrocarbyl" denotes a radical having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydro-carbon character within the context of thisinvention. Such radicals include the following:

(1) Hydrocarbon radicals; that is, aliphatic, (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic, aromatic-substituted aliphatic andalicyclic radicals, and the like, as well as cyclic radicals wherein thering is completed through another portion of the molecule (that is, anytwo indicated substituents may together form an alicyclic radical). Suchradicals are known to those skilled in the art; examples are

(2) Substituted hydrocarbon radicals; that is, radicals containingnon-hydrocarbon substituents which, in the context of this invention, donot alter the predominantly hydrocarbon character of the radical. Thoseskilled in the art will be aware of suitable substituents; examples are

(3) Hetero radicals; that is, radicals which, while predominantlyhydrocarbon in character within the context of this invention, containatoms other than carbon present in a chain or ring otherwise composed ofcarbon atoms. Suitable hetero atoms will be apparent to those skilled inthe art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about three substituents or hetero atoms, andpreferably no more than one, will be present for each 10 carbon atoms inthe hydrocarbyl radical.

Terms such as "alkyl-based radical", "aryl-based radical" and the likehave meaning analogous to the above with respect to alkyl and arylradicals and the like.

Preferably, the hydrocarbyl radicals in the compounds of this inventionare free from acetylenic and usually also from ethylenic unsaturationand have about at least one carbon atom. The radicals are usuallyhydrocarbon and especially lower hydrocarbon, the word "lower" denotingradicals containing up to seven carbon atoms. They are preferably loweralkyl or aryl radicals, most often alkyl.

The novel polyamine condensates of the present invention are prepared bythe acid catalyzed condensation reaction of the hydroxy alkyl or hydroxyaryl reactant (II) with the amine reactant (III) at an elevatedtemperature.

The amine reactants, as represented by Formula (III) above, arecharacterized by the presence within their structure of the R-N groupwherein R is described hereinabove and are lower molecular weightpolyamines. Mixtures of two or more amines can be used in the reactionwith one or more hydroxy alkyl or hydroxy aryl reactants which arewithin the scope of this invention. The amine reactants of the presentinvention may contain aliphatic, cycloaliphatic, aromatic, orheterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted heterocyclic, cycloaliphatic substitutedaliphatic, cycloaliphatic-substituted aromatic,cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic,aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substituted alicyclic,and heterocyclic-substituted aromatic groups and may contain unsaturatedsites in the molecule. If the amine contains such unsaturated sites,such unsaturation will not be acetylenic. These amines may also containnon-hydrocarbon substituents or groups as long as these groups do notsignificantly interfere with the reaction of the amines with the hydroxyalkyl or hydroxy aryl reactants of the invention. Such non-hydrocarbonsubstituents or groups include lower alkoxy, lower alkyl mercapto,nitro, interrupting groups such as --O--and--S-- (e.g., as in suchgroups as --CH₂ CH₂ --X--CH₂ CH₂ -- where X is --O-- or --S--).

Examples of suitable polyamine reactants according to the presentinvention include N-amino-propyl-cyclohexylamines,N-N'-di-n-butyl-para-phenylene diamine, bis-(para aminophenyl)methane,1,4-diaminocyclohexane, and the like.

Heterocyclic polyamines can also be used as (III) in preparing thecompositions of this invention. As used herein, the terminology"heterocyclic polyamine(s)" is intended to describe those heterocyclicamines containing at least one nitrogen as a hetero atom in theheterocyclic ring. The heterocyclic amines (according to the presentinvention) can be saturated or unsaturated and can contain varioussubstituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl,aryl, alkaryl, or aralkyl substituents. Generally, the total number ofcarbon atoms in the substituents will not exceed about 20. Heterocyclicamines can contain more than one nitrogen hetero atom. The 5- and6-membered heterocyclic rings are preferred.

Among the suitable heterocyclic polyamines are aziridines, azetidines,azolidines, tetra- and di-hydro pyridines, pyrroles, indoles,piperidines, imidazoles, di- and tetra-hydroimidazoles, piperazines,isoindoles, purines, morpholines, thiomorpholines,N-aminoalkylmorpholines N-aminoalkylthiomorpholines,N-aminoalkylpiperazines, N,N'-di-aminoalkylpiperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Preferred heterocyclic amines are the saturated 5- and6-membered heterocyclic amines containing only nitrogen, oxygen and/orsulfur in the hetero ring, especially the piperidines, piperazines,thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine,aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substitutedpiperazines, morpholine, aminoalkyl-substituted morpholines,pyrrolidine, and aminoalkyl-substituted pyrrolidines, are especiallypreferred. Usually the aminoalkyl substituents are substituted on anitrogen atom forming part of the hetero ring. Specific examples of suchheterocyclic amines include aminopropylmorpholine, aminoethylpiperazine,and N,N'-di-aminoethylpiperazine.

Also suitable as amines are the aminosulfonic acids and derivativesthereof corresponding to the general formula: ##STR5## wherein R_(d) is-NH₂, alkali or alkaline earth metal, R_(a) is a polyvalent organicradical having a valence equal to x+y; R_(b) and R_(c) are eachindependently hydrogen, hydrocarbyl, and substituted hydrocarbyl withthe proviso that at least one of R_(b) or R_(c) is hydrogen peraminosulfonic acid molecule; x and y are each integers equal to orgreater than one. From the formula, it is apparent that each aminosulfonic reactant is characterized by at least one HN or H₂ N-- groupand at least one ##STR6## group. These sulfonic acids can be aliphatic,cycloaliphatic, or aromatic aminosulfonic acids and the correspondingfunctional derivatives of the sulfo group. Specifically, theaminosulfonic acids can be aromatic aminosulfonic acids, that is, whereR_(a) Y is a polyvalent aromatic radical such as phenylene where atleast one ##STR7## group is attached directly to a nuclear carbon atomof the aromatic radical. The aminosulfonic acid may also be a mono-aminoaliphatic sulfonic acid; that is, an acid where x is one and R_(a) is apolyvalent aliphatic radical such as ethylene, propylene, trimethylene,and 2-methylene propylene. Suitable aminosulfonic acids and derivativesthereof useful as the amine reactant (III) are disclosed in U.S. Pat.Nos. 3,029,250; 3,367,864; and 3,926,820; which are expresslyincorporated herein by reference for such disclosure.

The high molecular weight hydrocarbyl polyamines, which can be used asIII are generally prepared by reacting a chlorinated polyolefin having amolecular weight of at least about 400 with ammonia or the appropriateamine. Such amines are known in the art and described, for example, inU.S. Pat. Nos. 3,275,554 and 3,438,757, both of which are expresslyincorporated herein by reference for their disclosure in regard to howto prepare these amines.

Another group of amines suitable for use as amine reactant (III) arebranched polyalkylene polyamines. The branched polyalkylene polyaminesare polyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylenegroup.

These reactants may be expressed by the formula: ##STR8## wherein R isan alkylene group such as ethylene, propylene, butylene and otherhomologues (both straight chained and branched), etc., but preferablyethylene; and x, y and z are integers, x being for example, from 4 to 24or more but preferably 6 to 18, y being for example 1 to 6 or more butpreferably 1 to 3, and z being for example 0 to 6 but preferably 0 to 1.The x and y units may be sequential, alternative, orderly or randomlydistributed.

A preferred class of such polyamine reactants includes those of theformula ##STR9## wherein n is an integer, for example, 1-20 or more butpreferably 1-3, wherein R is preferably ethylene, but may be propylene,butylene, etc. (straight chained or branched).

U.S. Pat. Nos. 3,200,106 and 3,259,578 are expressly incorporated hereinby reference for their disclosure of how to make such polyamines.

Suitable amines also include polyoxyalkylene polyamines, e.g.,polyoxyalkylene diamines and polyoxyalkylene triamines, having averagemolecular weights ranging from about 200 to 4000 and preferably fromabout 400 to 2000. Illustrative examples of these polyoxyalkylenepolyamines may be characterized by the formula: ##STR10## wherein m hasa value of about 3 to 70 and preferably about 10 to 35. ##STR11##wherein n is such that the total value is from about 1 to 40 with theproviso that the sum of all of the n's is from about 3 to about 70 andgenerally from about 6 to about 35 and R is a polyvalent saturatedhydrocarbon radical of up to 10 carbon atoms having a valence of 3 to 6.The alkylene groups may be straight or branched chains and contain from1 to 7 carbon atoms, and usually from 1 to 4 carbon atoms. The variousalkylene groups present within Formulae VII and VIII may be the same ordifferent.

The preferred polyoxyalkylene polyamine reactants useful for thepurposes of this invention include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to 2000. Thepolyoxyalkylene polyamines are commercially available and may beobtained, for example, from the Jefferson Chemical Company, Inc. underthe trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.".

U.S. Pat. Nos. 3,804,763 and 3,948,800 are expressly incorporated hereinby reference for their disclosure of such polyoxyalkylene polyaminereactants.

Another preferred class of amine reactants for use in the presentinvention is alkylene polyamines, including the polyalkylene polyamines,which are described in more detail hereafter. The alkylene polyaminesinclude those conforming to the formula ##STR12## wherein n is from 1 toabout 10; each R" is independently a hydrogen atom, a hydrocarbyl groupor a hydroxy-substituted hydrocarbyl group having up to about 30 atoms,and the "Alkylene" group has from 1 to about 10 carbon atoms, but thepreferred alkylene is ethylene or propylene. Especially preferred arethe alkylene polyamines where each R" is hydrogen with the ethylenepolyamines and mixtures of ethylene polyamines being the most preferred.Usually n will have an average value of from about 2 to about 7. Suchalkylene polyamines include methylene polyamine, ethylene polyamines,butylene polyamines, propylene polyamines, pentylene polyamines,hexylene polyamines, heptylene polyamines, etc. The higher homologs ofsuch amines .and related aminoalkylsubstituted piperazines are alsoincluded.

Alkylene polyamines useful in preparing the carboxylic derivativecompositions include ethylene diamine, triethylene tetramine, propylenediamine, trimethylene diamine, hexamethylene diamine, decamethylenediamine, octamethylene diamine, di(heptamethylene)triamine, tripropylenetetramine, tetraethylene pentamine, trimethylene diamine, pentaethylenehexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine,1,4-bis(2-aminoethyl)piperazine, and the like. Higher homologs, as areobtained by condensing two or more of the above-illustrated alkyleneamines, are useful as reactant (III) as are mixtures of two or more ofany of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are especiallyuseful for reasons of cost and effectiveness. Such polyamines aredescribed in detail under the heading "Diamines and Higher Amines" inThe Encyclopedia of Chemical Technology, Second Edition, Kirk andOthmer, Volume 7, pages 27-39, Interscience Publishers, Division of JohnWiley and Sons, 1965, which is hereby incorporated by reference fortheir disclosure of useful polyamines. Such compounds are prepared mostconveniently by the reaction of an alkylene chloride with ammonia or byreaction of an ethylene imine with a ring-opening reagent such asammonia, etc. These reactions result in the production of the somewhatcomplex mixtures of alkylene polyamines, including cyclic condensationproducts such as piperazines.

Other useful types of polyamine reactant mixtures are those resultingfrom stripping of the above-described polyamine mixtures. In thisinstance, lower molecular weight polyamines and volatile contaminatesare removed from an alkylene polyamine mixture to leave as residue whatis often termed "polyamine bottoms". In general, alkylene polyaminebottoms can be characterized as having less than two, usually less than1% by weight material boiling below about 200° C. In the instance ofethylene polyamine bottoms, which are readily available and found to bequite useful, the bottoms contain less than about 2% by weight totaldiethylene triamine (DETA) or triethylene tetramine (TETA). A typicalsample of such ethylene polyamine bottoms obtained from the Dow ChemicalCompany of Freeport, Tex. designated "E-100" showed a specific gravityat 15.6° C. of 1.0168, a percent nitrogen by weight of 33.15 and aviscosity at 40° C. of 121 centistokes. Gas chromatography analysis ofsuch a sample showed it to contain about 0.93% "Light Ends" (DETA),0.72% TETA, 21.74% tetraethylene pentamine and 76.61% pentaethylenehexamine and higher (by weight). These alkylene polyamine bottomsinclude cyclic condensation products such as piperazine and higheranalogs of diethylene triamine, triethylene tetramine and the like.

A preferred group of polyamine reactants useful for the presentinvention includes polyamines of formula (II): ##STR13## in which each Ris hydrogen or a hydrocarbyl group; each R' is independently hydrogen,alkyl, or NH₂ R"(NR")_(y) - wherein each R" is independently an alkylenegroup of 1 to about 10 carbon atoms and y is a number in the range offrom 1 to about 6; each Z is independently an alkylene group of 1 toabout 10 carbon atoms, a heterocyclic nitrogen containing cycloalkyleneor an oxyalklene group of 1 to about 10 carbon atoms and x is a numberin the range of from 1 to about 10.

The hydroxy alkyl and hydroxy aryl reactants as represented by Formula(II) hereinabove are preferably polyhydroxy materials which willcondense with the above discussed amine reactants and more preferablywill condense to very high molecular weight materials as opposed toforming cyclic products. The hydroxy containing reactant may be selectedfrom aliphatic, cycloaliphatic, and aryl based radicals wherein theradical is preferably an alkyl based radical and most preferably ahydroxyethyl radical. These hydroxy containing materials may containother functional groups so long as they do not interfere with thecondensation with the amine reactant or adversely affect the propertiesof the resultant high molecular weight polyamine condensate.

Aside from the above-discussed limitations on the hydroxy containingreactant, this reactant may be selected from numerous hydroxy containingcompounds or species. Inclusive, but not exclusive thereof, of suchhydroxy containing materials there may be mentioned, polyalkylenepolyols, alkylene glycols and polyoxyalkylene polyols such aspolyoxyethylene polyols, polyoxypropylene polyols, polyoxybutylenepolyols, and the like. These polyoxyalkylene polyols (sometimes calledpolyglycols) can contain up to about 150 oxyalkylene groups wherein thealkylene radical contains from 2 to about 8 carbon atoms. Suchpolyoxyalkylene polyols are generally dihydric alcohols. That is, eachend of the molecule terminates with an -OH group. In order for suchpolyoxyalkylene alcohols to be useful as a reactant, there must be atleast two such --OH groups. The monoethers of these alkylene glycols andpolyoxyalkylene glycols are also useful as reactants. These include themonoaryl ethers, monoalkyl ethers, and monoaralkyl ethers of thesealkylene glycols and polyoxyalkylene glycols. This group of alcohols maybe represented by the general formula ##STR14## wherein R_(C) is arylsuch as phenyl, lower alkoxy phenyl, or lower alkyl phenyl; lower alkylsuch as ethyl, propyl, tert-butyl, pentyl, etc.,; and aralkyl such asbenzyl, phenylethyl, phenylpropyl, p-ethyl-phenylethyl, etc.; p is zeroto about 150, and R_(A) and R_(B) are lower alkylene of 2 to about 8carbon atoms and, preferably, 2 to 4 carbon atoms. Polyoxyalkyleneglycols where the alkylene groups are ethylene or propylene and p is atleast two as well as the monoethers thereof as described above areconsidered very useful for the purposes of the present invention.

The aryl polyhydric alcohols useful as the hydroxy reactant includepolyhydric phenols and naphthols, which are the preferredhydroxyaromatic compounds. These hydroxy-substituted aromatic compoundsmay contain other substituents in addition to the hydroxy substituentssuch as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like.Usually, the hydroxy aromatic compound will contain 1 to 4 hydroxygroups. The aromatic hydroxy compounds are illustrated by the followingspecific examples: beta-naphthol, p-nitrophenol, alpha-naphthol,cresols, resorcinol, catechol, thymol, eugenol, p,p'-dihydroxy-biphenyl,hydroquinone, pyrogallol, phloroglucinol, hexyl-resorcinol, resorcinol,guaiacol, alpha-decylbeta-naphthol, the condensation product of heptylphenol with 0.5 moles of formaldehyde, the condensation product ofoctylphenol with acetone, di(hydroxyphenyl) oxide,di(hydroxyphenyl)sulfide, di-(hydroxyphenyl) disulifde.

Other specific alcohols useful as the hydroxy containing reactant arethe ether alcohols and amino alcohols including, for example, theoxyalkylene, oxy-arylene-, amino-alkylene-, andamino-arylene-substituted alcohols having one or more oxyalkylene,aminoalkylene or amino-aryleneoxy-arylene radicals. They are exemplifiedby Cellosolve, carbitol, mono-(heptylphenyloxypropylene)substitutedglycerol, poly(styreneoxide), aminoethanol, di(hydroxyethyl)amine,tri(hydroxypropyl)amine, N,N,N',- N'-tetrahydroxytrimethylenediamine,and the like.

The polyhydric alcohol reactants of the present invention preferablycontain from 2 to about 10 hydroxy radicals. They are illustrated, forexample, by the alkylene glycols and polyoxyalkylene glycols mentionedabove such as ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, tripropylene glycol,dibutylene glycol, tributylene glycol, and other alkylene glycols andpolyoxyalkylene glycols in which the alkylene radicals contain 2 toabout 8 carbon atoms.

A preferred class of alcohols suitable as reactant (II) are thosepolyhydric alcohols containing up to about 12 carbon atoms, andespecially those containing 3 to 10 carbon atoms. This class of alcoholsincludes glycerol, erythritol, pentaerythritol, dipentaerythritol,gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptanediol,2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,1,2,4-butanetriol, 2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol,1,10-decanediol, digitalose, and the like. Aliphatic alcohols containingat least three hydroxyl groups and up to five hydroxyl groups areparticularly preferred.

Amino alcohols contemplated as suitable for use as the hydroxycontaining reactant have two or more hydroxy groups. Examples ofsuitable amino alcohols are the N-(hydroxy-lower alkyl)amines andpolyamines such as di-(2-hydroxyethyl)-amine,tri-(2-hydroxyethyl)-amine, N,N,N'-tri-(2-hydroxyethyl)ethylenediamine,N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone, and ethers thereof withaliphatic alcohols, especially lower alkanols,N,N-di-(3-hydroxypropyl)glycine, and the like. Also contemplated areother poly-N-hydroxyalkyl-substituted alkylene polyamines wherein thealkylene polyamine are as described above; especially those that contain2 to 3 carbon atoms in the alkylene radicals.

Polyoxyalkylene polyols which have two or three hydroxyl groups andmolecules consisting essentially of hydrophobic portions comprising##STR15## groups wherein R_(D) is lower alkyl of up to three carbonatoms and hydro-philic portions comprising --CH₂ CH₂ O-- groups are apreferred hydroxy continuing reactant. Such polyols can be prepared byfirst reacting a compound of the formula R_(E) (OH)_(q) where q is 2-3and R_(E) is hydrocarbyl with a terminal alkylene oxide of the formula##STR16## and then reacting that product with ethylene oxide. R_(E)(OH)_(q) can also be, for example, (trimethylolpropane),(trimethylolethane), ethylene glycol, trimethylene glycol,tetramethylene glycol, tri-(beta-hydroxypropyl)amine,1,4-(2-hydroxyethyl)-cyclohexane, (tris-(hydroxymethyl)amino methane,2-amino-2-methyl-1,3-propane diol,N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene diamine,N,N,N',N'-tetrakis(2-hydroxyethyl)-ethylene diamine, resorcinol, or oneof the other illustrative examples mentioned hereinbefore. The foregoingdescribed R_(E) (OH)_(q) polyols may also be used alone as the hydroxycontaining (II) reactant.

Other hydroxy containing reactants useful in the present invention arehydroxyalkyl, hydroxy alkyl oxyalkyl and hydroxy aryl sulfides of theformula

    S.sub.f (R.sub.f OH).sub.2f                                (X)

wherein f is 1 or 2 and R_(F) is alkyl of 1 to about 10 carbon atomsalkyl oxyalkyl where alkyl is 1 to about 10 carbon atoms and preferably2 to 4 carbon atoms, and aryl of at least 6 carbon atoms. For thepurposes of the present invention, 2,2'-thiodiethanol and2,2'-thiodipropanol are the preferred reactants for this class ofhydroxy containing reactants.

Preferred combinations of reactant for making the polyamines of thepresent invention include those in which reactant (A) is a polyhydricalcohol of formula (II) having three hydroxy groups or an amino alcoholof formula (II) having two or more hydroxy groups and reactant (B) is analkylene polyamine having at least two primary nitrogen atoms andwherein the alkylene group contains 2 to about 10 carbon atoms; andwherein the reaction is conducted in the presence of an acid catalyst atan elevated temperature.

As indicated previously, the reaction of the amine reactant with thehydroxy alkyl or hydroxy aryl reactant requires the presence of an acidcatalyst. Those catalysts useful for the purpose of this inventioninclude mineral acids (mono, di- and poly basic acids) such as sulfuricacid and phosphoric acid; organo phosphorus acids and organo sulfonicacids such as R*P(0)(OH)₂ and R*SO₃ H, wherein R* is hydrocarbyl; alkalimetal partial salts of H₃ PO₄ and H₂ SO₄, such as NaHSO₄, LiHSO₄, KHSO₄,NaH₂ PO₄, LiH₂ PO₄ and KH₂ PO₄ ; alkaline earth metal partial salts ofH₃ PO₄ and H₂ SO₄, such as CaHPO₄, CaSO₄ and MgHPO₄ ; also Al₂ O₃ andZeolites. Phosphoric acid is preferred because of its commercialavailability and ease of handling. Also useful as catalysts for thisinvention are materials which generate acids when treated in thereaction mixture, e.g., triphenylphosphite.

The reaction is run at an elevated temperature which, depending upon theparticular reactants, can range from 60° C. to about 265° C. Mostreactions, however, are run in the 220° C. to about 250° C. range.Furthermore, this reaction may be run at atmospheric pressure oroptionally at a reduced pressure depending upon the particular reactantsand the concomitant economics. The degree of condensation of theresultant high molecular weight polyamine prepared by the process of thepresent invention is limited only to the extent to prevent the formationof solid products under reaction conditions. The control of the degreeof condensation of the product of the present invention is normallyaccomplished by limiting the amount of the condensing agent, i.e., thehydroxy alkyl or hydroxy aryl reactant charged to the reaction medium.In a preferred embodiment, the condensed high molecular weightpolyamines of the present invention are pourable at room temperature andhave viscosities which range from about 100% greater than the viscosityof the amine reactant (III) to about 6000% greater than the viscosity ofthe amine reactant (III). In another preferred embodiment, the condensedhigh molecular weight polyamines of the present invention haveviscosities which range from 50% to about 1000% greater than theviscosity of the amine reactant (III). In a most preferred embodiment,the viscosity of these polyamines will range from about 50 cSt to about200 cSt at 100° C. It is pointed out that the foregoing limitation onthe degree of condensation of the products of the present invention issolely for the purpose of the ultimate end use of these materials inlubricant compositions. For other or related utilities, solid productsof the condensation reaction described above may be desirable and thusthe condensation may be carried out to result in high molecular weightsolid products where this may be accomplished by adjusting the relativeamounts of the respective reactants charged to the reaction medium.

The preparation of various high molecular weight polyamine condensatesrepresentative of products within the scope of the present invention isillustrated in the following examples. While these examples will showone skilled in the art how to operate within the scope of thisinvention, they are not to serve as a limitation on the scope of theinvention where such scope is defined only in the claims. It is pointedout that in the following examples, and elsewhere in the presentspecification and claims, all percentages and all parts are intended toexpress percent by weight and parts by weight unless otherwise clearlyindicated.

EXAMPLE I

A 4-necked, 500-ml, round-bottom flask equipped with glass stirrer,thermowell, subsurface N₂ inlet, Dean-Stark trap, and Friedrichcondenser was charged with

a) 201 grams of Tetraethylenepentamine (TEPA).

b) 151 grams of 40% aqueous Tris(hydroxymethyl)aminomethane (THAM), and

c) 3.5 grams of 85% H₃ PO₄.

The mixture was heated to 120° C. over 1.0 hour. With N₂ sweeping, themixture was heated to 130° C. over 1 hour and to 230° C. over 2 hoursmore. Held at 230°-240° C. for 4 hours and at 241°-250° C. for 3 hours.The product was cooled to 150° C. and filtered with diatomaceous earthfilter aid.

EXAMPLE II

A 4-necked, 3-1, round-bottom flask was equipped with glass stirrer,thermowell, subsurface N₂ inlet, Dean-Stark trap, and Friedrichcondenser was charged with:

a) 1299 grams of HPA Taft Amines (amine bottoms).

b) 727 grams of 40% aqueous Tris(hydroxymethyl)aminomethane (THAM).

The mixture was heated to 60° C. and 23 grams of 85% H₃ PO₄ was added.The mixture was heated to 120° C. over 0.6 hr. With N₂ sweeping, themixture was heated to 150° C. over 1.25 hr. and to 235° C. over 1 hr.more. Held at 230°-235° C. for 5 hr. Heated to 240° C. over 0.75 hr. andheld at 240°-245° C. for 5 hr. The product was cooled to 150° C. andfiltered with a diatomaceous earth filter aid. Yield: 84% (1221 grams).

EXAMPLE III

A 3-liter flask equipped with stirrer, thermowell, below surface N₂inlet and a stripping condenser was charged with 363 grams of THAM and1200 grams of TEPA. Next was added 16 grams of H₃ PO₄ at 110° C. N₂blowing was commenced at 0.25 cfh. The mixture was then heated to 220°C. in 0.8 hour and held at 220-225° C. for 1.2 hour; then heated to 230°C. in 0.2 hour and held at 230° C. for 4.75 hours: 129 g distillatecollected. The mixture stood and was held at 242°-245° C. for 5 hours:39 g of additional distillate was collected in trap. Held at 246°-255°C. for 1.2 hr: 178 g material in trap; NNBbpb=170. The mixture wasfiltered at 155° C. using 45 g of a diatomaceous earth filter aid.

EXAMPLE IV

A 3-liter flask equipped with stirrer, thermowell, below surface N₂inlet and a stripping condenser was charged with 363 grams of THAM and1200 grams of TEPA. 16 grams of H₃ PO₄ was added at 100° C. N₂ blowingwas commenced at 0.2 cfh. The mixture was heated to 165° C. in 0.4 hour;and to 241° C. in 0.6 hour. Held at 241°-243° C. for 0.3 hour. Thecontents were further heated to 250° C. an additional 0.5 hour and heldat 250° C. for 5.5 hour: 288 g of material was collected in the trap;NNBbpb=506. This material was filtered at 150° C. using 55 g ofdiatomaceous earth filter aid.

EXAMPLE V

A 1-liter flask equipped with stirrer, thermowell, below surface N₂inlet and Dean-Stark trap was charged with 121 grams of THAM and 400grams of TEPA. To this mixture was added 8.2 grams of KH₂ PO₄ at 60° C.N₂ blowing was commenced at a 0.15 cfh. The reaction mixture was heatedto 150° C. over 1 hour to 230° C. and over another 1.5 hours. Thetemperature was held at 230° C.-232° C. for 4.25 hour: 17 g materialcollected in trap. The heated mixture was allowed to stand and was heldat 237° C. for 3.25 hour: 38 g material collected in trap. The mixturewas further heated to 241° C. over 0.75 hour and held at 241° C.-242° C.for 4.75 hr.: 50 g of material collected in trap. The material wasallowed to stand and then held at 250° C. for 5 hour: total of 53 gmaterial collected in trap: NNBbph=96.5. Filtered at 150° C. using 20 gof diatomaceous earth filter aid.

EXAMPLE VI

To a 500 ml flask equipped with stirrer, thermowell, below surface N₂inlet to Dean-Stark trap was charged with 201 grams of TEPA and 468grams of gylcerol. 2.3 grams H₃ PO₄ were added at 80° C. N₂ blowing wascommenced at 0.35 cfh. The mixture was heated to 220° C. over 2 hours;to 240° C. in 1 hour; to 245° C. in 1.5 hour and to 255° C. in 1 hour.The temperature was held at 255°-252° C. for 2 hours: 12 g materialcollected in trap. The mixture was allowed to stand and held at255°-262° C. for 7 hours: 34 g material collected in trap. Thetemperature of the mixture was further held at 255°-260° C. for 1 hourmore. A total of 36 g collected in trap: NNBbph=435. Filtered at 130° C.using 23 g of diatomaceous earth filter aid.

EXAMPLE VII

To a 500 ml flask equipped with stirrer, thermowell, below surface N₂inlet and Dean-Stark trap was charged 201 grams of TEPA and 45 grams ofhexaglycerol. To this mixture 3.5 grams of H was added at 85° C. N₂blowing was commenced at 0.35 cfh. The mixture was heated to 245° C.over 0.7 hour and held at 245° C.-260° C. for 1.75 hour: 10 g ofmaterial collected in trap. The mixture was allowed to stand and held at260° C.-270° C. for 7.5 hour: total of 27 g of material collected intrap: NNBbph=645. Filtered at 125° C. using 20 g of diatomaceous earthfilter aid.

Highly Condensed Polyamines Further Reacted To Form Dispersant Materials

While the high molecular weight condensed polyamines of the presentinvention are useful by themselves as lubricant and fuel additives anddispersants, they may be further reacted to form even higher molecularweight lubricant and fuel dispersant materials. In general, materialswhich may be used to further react with polyamine materials of thepresent invention are materials known to those skilled in the art andare described in numerous books, articles and patents. A number of thesereference materials are noted hereinbelow in relation to specific typesof dispersants and, where this is done, it is to be understood that theyare incorporated by reference for their disclosures relevant to thesubject matter discussed at the point in the specification in which theyare identified.

CARBOXYLIC ACID OR PHENOL REACTANT MATERIALS

Among the reactant materials that may be used for the purposes of thepresent invention to react with the above-described polyamines to formthe higher molecular weight dispersant materials, there may be firstmentioned carboxylic acids. The carboxylic acids from which suitableneutral and basic salts for use in this invention can be made includealiphatic, cycloaliphatic, and -aromatic mono- and polybasic carboxylicacids such as the naphthenic acids, alkyl- or alkenyl-substitutedcyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids,alkyl- or alkenyl-substituted aromatic carboxylic acids. The aliphaticacids generally contain at least eight carbon atoms and preferably atleast twelve carbon atoms. Usually, they have no more than about 400carbon atoms. Generally, if the aliphatic carbon chain is branched, theacids are more oil-soluble for any given carbon atoms content. Thecycloaliphatic and aliphatic carboxylic acids can be saturated orunsaturated. Specific examples include 2-ethylhexanoic acid, -linolenicacid, propylene-tetramer-substituted maleic acid, behenic acid,isostearic acid, pelargonic acid, capric acid, palmitoleic acid,linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecyclicacid, dioctylcyclopentane carboxylic acid, myristic acid,dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, commercially available mixtures of twoor more carboxylic acids such as tall oil acids, rosein acids and thelike.

A preferred group of oil-soluble carboxylic acids useful in preparingthe salts used in the present invention are the oil-soluble aromaticcarboxylic acids. These acids are represented by the general formulae:##STR17## where R* is an aliphatic hydrocarbon-based group of at leastfour carbon atoms, and no more than about 400 aliphatic carbon atoms, ais an integer of from one to four, Ar* is a polyvalent aromatichydrocarbon nucleus of up to about 14 carbon atoms, each X isindependently a sulfur or oxygen atom, and m is an integer of from oneto four with the proviso that R* and a are such that there is an averageof at least 8 aliphatic carbon atoms provided by the R* groups for eachacid molecule represented by Formula XIII. Examples of aromatic nucleirepresented by the variable Ar* are the polyvalent aromatic radicalsderived from benzene, naphthalene, anthracene, phenanthrene, indene,fluorene, biphenyl, and the like. Generally, the radical represented byAr* will be a polyvalent nucleus derived from benzene or naphthalenesuch as phenylenes and naphthylene, e.g., methylphenylenes,ethoxyphenylenes, nitrophenylenes, isopropylphenylenes,hydroxyphenylenes, mercaptophenylenes, N,N-diethylaminophenylenes,chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, andsimilar tri-, tetra-, penta-valent nuclei thereof, etc.

The R* groups are usually purely hydrocarbyl groups, preferably groupssuch as alkyl or alkenyl radicals. However, the R* groups can containsmall number substituents such as phenyl, cycloalkyl (e.g., cyclohexyl,cyclopentyl, etc.) and nonhydrocarbon groups such as nitro, amino, halo(e.g., chloro, bromo, etc.), lower alkoxy, lower alkyl mercapto, oxosubstituents (i.e.,=0), thio groups (i.e.,=S), interrupting groups suchas -NH-, --O--, --S-- and the like provided the essentially hydrocarboncharacter of the R* group is retained. The hydrocarbon character isretained for purposes of this invention so long as any non-carbon atomspresent in the R* groups do not account for more than about 10% of thetotal weight of the R* groups.

Examples of R* groups include butyl, isobutyl, pentyl, octyl, nonyl,dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethyoxypentyl,4-hexenyl, 3-cyclohexyloctyl, 4-(p-chloro-phenyl)-octyl,2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and substituents derivedfrom polymerized olefins such as polychloroprenes, polyethylenes,polypropylenes, polyisobutylenes, ethylene-propylene copolymers,chlorinated olefin polymers, oxidized ethylene-propylene copolymers andthe like. Likewise, the group Ar* may contain non-hydrocarbonsubstituents, for example, such diverse substituents as lower alkoxy,lower alkyl mercapto, nitro, halo, alkyl or alkenyl groups of less thanfour carbon atoms, hydroxy, mercapto and the like.

A group of particularly useful carboxylic acids are those of theformulae: ##STR18## where R*, X, Ar*, m and a are as defined in FormulaXIII and p is an integer of 1 to 4, usually 1 or 2. Within this group,an especially preferred class of oil-soluble carboxylic acids are thoseof the formulae: ##STR19## where R** in Formula X is an aliphatichydrocarbon group containing at least 4 to about 400 carbon atoms, a isan integer of from 1 to 3, b is 1 or 2, c is zero, 1, or 2 andpreferably 1 with the proviso that R** and a are such that the acidmolecules contain at least an average, of about twelve aliphatic carbonatoms in the aliphatic hydrocarbon substituents per acid molecule. Andwithin this latter group of oil-soluble carboxylic acids, thealiphatic-hydrocarbon substituted salicylic acids wherein each aliphatichydrocarbon substituent contains an average of at least about sixteencarbon atoms per substituent and one to three substituents per moleculeare particularly useful. Salts prepared from such salicylic acidswherein the aliphatic hydrocarbon substituents are derived frompolymerized olefins, particularly polymerized lower 1-mono-olefins suchas polyethylene, polypropylene, polyisobutylene, ethylene/propylenecopolymers and the like and having average carbon contents of about 30to about 400 carbon atoms.

The carboxylic acids corresponding to Formula XIII-XV above are wellknown or can be prepared according to procedures known in the art.Carboxylic acids of the type illustrated by the above formula andprocesses for preparing their neutral and basic metal salts are wellknown and disclosed, for example, in such U.S. Pat. Nos. as 2,197,832;2,197,835; 2,252,662; 2,252,664; 2,174,092; 3,410,798 and 3,595,791.

Another type of neutral and basic carboxylate salt used in thisinvention are those from alkenyl succinates of the general formula:##STR20## wherein R* is as defined above in Formula VIII. Such salts andmeans for making them are set forth in U.S. Pat. Nos. 3,271,130;3,567,637 and 3,632,510, which are hereby incorporated by reference inthis regard. An example of a desirable R* group is a polyalkylene groupcharacterized by an Mn value of 150 to about 5000 and Mw/Mn value ofabout 1.5 to about 4.0.

Other patents specifically describing techniques for making basic saltsof the hereinabove-described sulfonic acids, carboxylic acids, andmixtures of any two or more of these include U.S. Pat. Nos. 2,501,731;2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925;2,617,049; 2,777,874; 3,027,325; 3,256,186; 3,282,835; 3,384,585;3,373,108; 3,365,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809;3,471,403; 3,488,284; 3,595,790 and 3,629,109. The disclosures of thesepatents are hereby incorporated in this present specification for theirdisclosures in this regard as well as for their disclosure of specificsuitable basic metal salts.

Neutral and basic salts of phenols (generally known as phenates) arealso useful in the compositions of this invention and well known tothose skilled in the art. The phenols from which these phenates areformed are of the general formula: ##STR21## wherein R*, a, Ar*, X and mhave the same meaning and preferences as described hereinabove withreference to Formula XIII. The same examples described with respect toFormula XIII also apply.

A commonly available class of phenates are those made from phenols ofthe general formula: ##STR22## wherein a is an integer of 1-3, b is of 1or 2, z is 0 or 1, R' in Formula XIII is a substantially saturatedhydrocarbon-based substituent having an average of from 30 to about 400aliphatic carbon atoms and R⁴ is selected from the group consisting oflower alkyl, lower alkoxyl, nitro and halo groups.

One particular class of phenates for use in this invention are the basic(i.e., overbased, etc.) Group IIA metal sulfurized phenates made bysulfurizing a phenol as described hereinabove with a sulfurizing agentsuch as sulfur, a sulfur halide, or sulfide or hydrosulfide salt.Techniques for making these sulfurized phenates are described in U.S.Pat. Nos. 2,680,096; 3,036,971 and 3,775,321 which are herebyincorporated by reference for their disclosures in this regard.

Other phenates that are useful are those that are made from phenols thathave been linked through alkylene (e.g., methylene) bridges. These aremade by reacting single or multi-ring phenols with aldehydes or ketones,typically, in the presence of an acid or basic catalyst. Such linkedphenates as well as sulfurized phenates are described in detail in U.S.Pat. No. 3,350,038; particularly columns 6-8 thereof, which is herebyincorporated by reference for its disclosures in this regard.

Naturally, mixtures of two or more neutral and basic salts of thehereinabove described carboxylic acids and phenols can be used in thecompositions of this invention, including mixtures of two or more of anyof these.

The above-described reaction products form additive/dispersant materialsof the general formula:

    [(QT.sub.t).sub.v J.sub.j ]                                Formula XIX

wherein Q represents the non-reactive portion of the hereinabovedescribed carboxylic acid or phenol reactant material; T represents thereactive moiety of the particular carboxylic acid and/or phenol reactantwhich is acyl, acyloxy, oxyalklene, arylene or imidoyl; J represents thecondensed portion of the hereinabove described high molecular weightpolyamines; the same as defined herein; and t and j are independently awhole integer of at least 1.

The foregoing dispersants are generally prepared in the same manner asthe high molecular weight polyamines of the present invention. In otherwords, they are prepared by the acid catalyzed condensation reaction ofat least one of the high molecular weight polyamines of the presentinvention with at least one of the reactive materials describedhereinabove at an elevated temperature. The catalysts previouslydescribed herein are also useful in this reaction. These dispersantsgenerally have a total base number of about 45 to about 90, and moreparticularly in the range of about 55 to about 80.

In one embodiment, a high molecular weight additive/dispersant forlubricant and fuel compositions may be prepared by reacting

(A) hydrocarbyl substituted carboxylic acids or derivatives thereofcontaining at least about 34 carbon atoms with

(B) at least one polyamine reactant derived from a hydroxyalkyl orhydroxyaryl compound of the formula: ##STR23## wherein each R isindependently hydrogen or a hydrocarbyl, Y represents S, N, or O; A andX each independently represent an alkylene group; n is 0, 1 or 2dependent upon m and q, where q is 0 or 1 and m is 1, 2, or 3 and##STR24## wherein

each R is hydrogen or a hydrocarbyl group,

each R' is independently hydrogen, alkyl, or NH₂ R"(NR")_(y) - whereineach R" is independently an alkylene group of 1 to about 10 carbon atomsand y is a number in the range of from 1 to about 6,

each Z is independently an alkylene group of 1 to about 10 carbon atoms,a heterocyclic nitrogen containing cycloalkylene or oxyalkylene of 1 toabout 10 carbon atoms and

x is a number in the range of from 1 to about 10.

The additive dispersants made according to the aforementioned processexhibit a total base number in the range from about 3 to about 90 and,in one embodiment, may have a total base number in the range of fromabout 55 to about 85.

One embodiment of the additive dispersants made according to theaforementioned process having a base number in the range from 3 to about90 is at least one substituted succinic acid or derivative thereofconsisting of substituent groups and succinic groups wherein thesubstituent groups are derived from polyalkylene, said polyalkylenebeing characterized by a Mn value of 1,300 to about 5,000 and a Mw/Mnvalue of 1.5 to about 4.0, and wherein said polyamine is derive from ahydroxyalkyl or hydroxyaryl compound selected from the group consistingof glycerol, trimethylolpropane, trimethylolethane andtris(hydroxymethyl)aminomethane and an amine compound selected from thegroup consisting of a triethylenetetramine, diethylenetriamine,tetraethylenepentamine, pentaethylenehexamine and mixtures thereof.

Specifically, Q may be derived from a polyalkylenesubstitued succinicacid or derivative thereof wherein said polyalkylene substituent ischaracterized by a Mn value of 150 to about 5000 and a Mw/Mn value ofabout 1.5 to about 4.0.

The following examples are provided to illustrate various dispersantsprepared or derived from reaction of the polyamine materials of thepresent invention with such dispersant materials as described above.Again, it is emphasized that these examples are provided forillustrative purposes only and are not to serve as a limitation on thescope of the invention where such scope is set out solely in the claims.

EXAMPLE A

A 12-1, 4-necked, round-bottom flask equipped with stirrer, thermowell,subsurface N₂ inlet, Dean-Stark trap and Friedrich condenser was chargedwith (a) 460 g. TEPA/THAM(5N:1.50H) polyamine, H₃ PO₄ cat and (b) 2500g. 2C Dil oil. The mixture was heated to 105° C. and 3360 g. of apoly(isobutene) (molecular weight 1000)-substituted succinic anhydridehaving a saponification number of 100 was added through a funnel over1.5 hour. N₂ blowing was commenced slowly. The mixture was heat to 160°C. and held for 5.0 hours. The mixture was filtered at 150° C. withdiatomaceous earth filter aid to give the final product. Yield: 96%(5991 g), 40% 2C Dil oil. Analysis: % N=2.31/3=2.42; Free Amine=Nil;TBn(776)=49.1.

EXAMPLE B

A 12-1, 4-necked, round-bottom flask equipped with stirrer, thermowell,subsurface N₂ inlet, Dean-Stark trap and Friedrich condenser was chargedWith (a) 605 grams HPA Taft Amines/THAM(5N:1.20H) polyamine, H₃ PO₄ Catand (b) 3262 grams 2 c dil oil. The mixture was heated to 110° C. and4300 grams of a poly(isobutene)(molecular weight 1000)- substitutedsuccinic anhydride having a saponification number of 100 was addedthrough a funnel over 0.7 hour. N₂ blowing was commenced slowly. Themixture was heated to 160° C. over 1 hour and held at 160°-162° C. for 5hours. The mixture was filtered at 150° C. with diatomaceous earthfilter aid to give the final product. Yield: 96% (8155 g), 40% 2 c diloil. Analysis: %N =2.28/2.19; TBN(776) =46.5; TAN(744) =7.7.

EXAMPLE C

A 1-liter flask equipped with stirrer, thermowell and reflux condenserwas charged with 39 g of the reaction product of Example IV and 75 gMeOH. This mixture was heated and stirred clear solution at 40° C. Tothe mixture 2 c dil oil was added at 40° C. A solution of 218 g of apoly(isobutene)(molecular weight 1000)- substituted succinic anhydridehaving a saponification number of 100 in 110 g MePh was added over 0.8hour at 62°-50° C. This mixture was held at 50°-65° C. for 1 hour. Thismixture was stripped to 110° C. in 1.5 hour; to 120° C. in 1 hour; to160° C. in 0.8 hour more. N₂ blowing was commenced slowly at 0.15 cfhand held at 160° C. for 6.0 hours and then filtered at 150° C. using 25g of diatomaceous earth filter aid.

EXAMPLE D

To a 1-liter flask equipped with stirrer, thermowell, below surface N₂inlet and Dean-Stark trap was charged 4.6 g of the product of Example Iand 168 grams of a diluent oil. To this mixture was added 110 g of apoly(propylene)(molecular weight 168)- substituted succinic anhydridehaving a saponification number of 420 over 0.1 hour at 110° C.-135° C.(exc). N2 blowing was commenced slowly at 0.15 cfh. The mixture was heldat 130° C.-130° C. for 0.2 hour. The mixture was heated to 165° C. over0.8 hour and held at 165° C. for 4.5 hour. The mixture was allowed tostand. 56 g on Vcon LB625 was added. The mixture was filtered at 145° C.using 25 g of diatomaceous earth filter aid.

EXAMPLE E

A 1-liter flask equipped with stirrer, thermowell, powder funnel andDean-Stark trap was charged with 44.3 g of the product of Example VI and2 c dil oil. To this mixture was added 336 g of apoly(isobutene)(molecular weight 1000) substituted succinic anhydridehaving a saponification number of 100 was added over 0.7 hour at 105° C.N₂ blowing was commenced slowly at 0.35 cfh. This mixture was heated to160° C. over 1 hour, held at 160° C.- 162° C. for 5.5 hours. Thismixture was filtered at 150° C. using 30 g diatomaceous earth filteraid.

EXAMPLE F

A 1-liter flask equipped with stirrer, thermowell, below surface N₂inlet and Dean-Stark trap was charged with 50.3 g of the product ofExample VII and 2 c dil oil. To this mixture was added 336 g of apoly(isobutene)(molecular weight 1000) substituted succinic anhydridehaving a saponification number of 100 which was added over 0.9 hour at110° C. N₂ blowing was commenced slowly at 0.35 cfh. This mixture washeated to 160° C. over 0.6 hour and held at 160°-163° C. for 5 hour.This mixture was filtered at 150° C. using 22 g of diatomaceous earthfilter aid.

EXAMPLE G

A 1-liter flask equipped with stirrer, thermowell, reflux condenser wascharged with 224 grams of a poly(isobutene)(molecular weight 1000)-substituted Phenol To the mixture was added 13.2 g. (CH₂ O)_(x),n-butanol to 1.6 g. NaOH solution at 72° over 0.15 hr. The mixture washeld at 72° C. for 5 hr. (a clear solution was observed after 4.5 hr.).To the mixture was added 25 g. HCl solution to give a neutral solution.To this mixture was added 13.9 grams 1074-27181 over 0.1 hour. Themixture was heated to 110° C. over 1.2 hr. (began removing distillate).The mixture was heated to 120° C. in 0.4 hr. and to 158° C. in 0.6 hrmore. The mixture was held at 158°-160° C. for 0.8 hr. The mixture wasallowed to stand and held at 160° C. for 5 hr. The mixture was strippedto 160° C. in 30 mm. The mixture was filtered at 150° C. using 22 g DD1600. Filtered material is produced.

The foregoing examples illustrate high TBN (45-50) dispersants, whichsurprisingly exhibit a low free amine content of less than .1 andprepared using the high molecular weight condensed polyamines of thepresent invention, show better engine test performance than productsprepared from more conventional amines, e.g., amine bottoms,tetraethylene amines, and the like. Furthermore, these products givemore thermally stable dispersants exhibiting a TBN as high as 77, 40%dilution. However, low TBN dispersants, which exhibit improvedperformance, may also be prepared according to the present invention.

The above compositions of the invention can be employed in a variety oflubricants based on diverse oils of lubricating viscosity, includingnatural and synthetic lubricating oils and mixtures thereof. Theselubricants include crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, including automobileand truck engines, two-cycle engines, aviation piston engines, marineand railroad diesel engines, and the like. They can also be used in gasengines, stationary power engines and turbines and the like. Automatictransmission fluids, transaxle lubricants, gear lubricants,metal-working lubricants, hydraulic fluids and other lubricating oil andgrease compositions can also benefit from the incorporation therein ofthe compositions of the invention.

Natural oils include animal oils and vegetable oils (e.g., castor, lardoil) liquid petroleum oils and hydrorefined, solvent-treated oracid-treated mineral lubricating oils of the paraffinic, naphthenic andmixed paraffinic-naphthenic types. Oils of lubricating viscosity derivedfrom coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halo-substitutedhydrocarbon oils such as polymerized and interpolymerized olefins [e.g.,polybutylenes, polypropylenes, propylene-isobutylene copolymers,chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes),poly(1decenes)]; alkylbenzenes (e.g., dodecylbenzenes,tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes);polyphenyls (e.g., biphenyls, terphyenyls, alkylated polyphenols); andalkylated diphenyl ethers and alkylated diphenyl sulfides and thederivatives, analogs and homologs thereof.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherifications, etc., constitute another class of known syntheticlubricating oils. These are exemplified by polyoxyalkylene polymersprepared by polymerization of ethylene oxide or propylene oxide, thealkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,methylpolyisopropylene glycol ether having an average molecular weightof 1000, diphenyl ether of polyethylene glycol having a molecular weightof 500-1000, diethyl ether of polypropylene glycol having a molecularweight of 1000-1500); and mono- and polycarboxylic esters thereof, forexample, the acetic acid esters, mixed C₃ -C₈ fatty acid esters and C₁₃Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with avariety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonether, propylene glycol). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, and the complex ester of linoleic acid dimer, andthe complex ester formed by reacting one mole of sebacic acid with twomoles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylolpropane, pentaerythritol, dipentaerythritol andtripentaerythritol.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxysiloxane oils and silicate oils comprise another useful classof synthetic lubricants; they include tetraethyl silicate,tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate,tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tertbutylphenyl)silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanesand poly(methylphenyl) siloxanes. Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid)and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants ofthe present invention. Unrefined oils are those obtained directly from anatural or synthetic source without further purification treatment. Forexample, a shale oil obtained directly from retorting operations, apetroleum oil obtained directly from distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques, such as distillation, solvent extraction, acidor base extraction, filtration and percolation are known to thoseskilled in the art. Rerefined oils are obtained by processes similar tothose used to obtain refined oils applied to refined oils which havebeen already used in service. Such rerefined oils are also known asreclaimed or reprocessed oils and often are additionally processed bytechniques for removal of spent additives and oil breakdown products.

Generally the lubricants of the present invention contain a lubricatingimproving amount of one or more of the compositions of this invention,e.g., sufficient to provide it with improved detergent/dispersant and/orV.I. properties. Normally the amount employed will be about 0.05% toabout 20%, preferably about 0.1% to about 10% of the total weight of thelubricating composition. This amount is exclusive of solvent/diluentmedium. In lubricating compositions operated under extremely adverseconditions, such as lubricating compositions for marine diesel engines,the metal salts of this invention may be present in amounts of up toabout 30% by weight, or more, of the total weight of the lubricatingcomposition.

The invention also contemplates the use of other additives incombination with the compositions of this invention. Such additivesinclude, for example, detergents and dispersants of the ash-producing orashless type, corrosion- and oxidation-inhibiting agents, pour pointdepressing agents, extreme pressure agents, antiwear agents, colorstabilizers and anti-foam agents.

Many of the above-mentioned extreme pressure agents and corrosionoxidation inhibitors also serve as antiwear agents. Zincdialkylphosphorodithioates are a well know example.

Pour point depressants are a particularly useful type of additive oftenincluded in the lubricating oils described herein. The use of such pourpoint depressants in oil-based compositions to improve low temperatureproperties of oil-based compositions is well known in the art. See, forexample, page 8 of "Lubricant Additives" by C. V. Smalheer and R.Kennedy Smith (Lezius-Hiles Co., publishers, Cleveland, Ohio, 1967).

Examples of useful pour point depressants are polymethacrylates,polyacrylates; polyacrylamides; condensation products of haloparaffinwaxes and aromatic compounds; vinyl carboxylate polymers; andterpolymers of dialkylfumarates, vinylesters of fatty acids andalkylvinylethers. Pour point depressants useful for the purpose of thisinvention, techniques for their preparation and their uses are describedin U. S. Pat. Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022;2,191,498; 2,666,746; 2,721,877; 2,721,878 and 3,250,715 which arehereby incorporated by reference for their relevant disclosures.

Anti-foam agents are used to reduce or prevent the formation of stablefoam. Typical anti-foam agents include silicones or organic polymers.Additional antifoam compositions are described in "Foam Control Agents",by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.

The compositions of this invention can be added directly to the fuels orlubricants. Preferably, however, they are diluted with a substantiallyinert, normally liquid organic diluent such as mineral oil, naphtha,benzene, toluene or xylene, to form an additive concentrate. Theseconcentrates usually contain from about 10% to 80% by weight of thecomposition of this invention, and 20% to 90% by weight of the inertdiluents. The concentrates also may contain one or more other additivesknown in the art or described hereinabove.

The fuel compositions of the present invention contain a majorproportion of a normally liquid fuel, usually a hydrocarbonaceouspetroleum distillate fuel such as motor gasoline as defined by ASTMSpecification D439 and diesel fuel or fuel oil as defined by ASTMSpecification D396. Normally liquid fuel compositions comprisingnon-hydrocarbonaceous materials such as alcohols, ethers, organo-nitrocompounds and the like (e,g., methanol, ethanol, diethyl ether, methylethyl ether, nitromethane) are also within the scope of this inventionas are liquid fuels which are mixtures of one or more hydrocarbonaceousfuels and one or more non-hydrocarbonaceous materials are alsocontemplated. Examples of such mixtures are combinations of gasoline andethanol and of diesel fuel and ether. Particularly preferred isgasoline, that is, a mixture of hydrocarbons having an ASTM distillationrange from about 60° C. at the 10% distillation point to about 205° C.at the 90% distillation point.

Generally, these fuel compositions contain an amount of the fueladditive of this invention sufficient to improve one or more propertiesof the fuel such as rustinhibition, dispersancy, etc.; usually thisamount is about 0.005% to about 0.5% by volume, preferably about 0.01%to about 0.1% by volume, based on the volume of such fuel compositions.

The fuel compositions can contain, in addition to the fuel additivecompositions of this invention, other additives which are well known tothose of skill in the art. These include antiknock agents such astetraalkyl lead compounds, lead scavengers such as haloalkanes (e.g.,ethylene dichloride and ethylene dibromide), deposit preventers ormodifiers such as triaryl phosphates, dyes, cetane improvers,antioxidants such as 2,6-di-tertiarybutyl-4 methylphenol, rustinhibitors such as alkylated succinic acids and anhydrides,bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers,upper cylinder lubricants and anti-icing agents.

The fuel additive compositions of this invention can be added directlyto the fuel, or they can be diluted with a substantially inert, normallyliquid organic diluent such as naphtha, benzene, toluene, xylene or anormally liquid fuel as described above, to form an additiveconcentrate. These concentrates generally contain from about 20% toabout 90% by weight of the composition of this invention and maycontain, in addition one or more other conventional additives known inthe art or described hereinabove.

The fuel additive compositions of this invention can be provided inconcentrate form with less than the aboveindicated levels of additives,and then be added directly to the fuel along with additional amounts ofthe compositions of this invention and other known additives, or befurther diluted with additives prior to the addition to the fuel untilthe level of additives is at the desired level.

What is claimed is:
 1. A polyamine comprising units of the formula:##STR25## wherein R is independently hydrogen or C₁₋₇ hydrocarbyl; R' ishydrogen, alkyl or NH₂ R"(NR")_(y), wherein y is a number in the rangefrom 1 to about 6 and R" is an alkylene group of 1 to about 10 carbonatoms; Y represents N or O; X is an alkylene group; A is hydrocarbyl; Zis a heterocyclic ring containing at least one nitrogen atom; x is anumber in the range from 1 to about 10; u is an integer greater than 1;and n is 0 or
 1. 2. The polyamine as defined in claim 1 wherein saidunits comprise: ##STR26## wherein R, R¹ Z, x and u are the same asdefined in claim
 1. 3. A lubricating composition comprising a majoramount of an oil of lubricating viscosity and a minor amount of thepolyamine f claim
 1. 4. A lubricating composition comprising a majoramount of an oil of lubricating viscosity and a minor amount of theproduct of claim
 2. 5. An additive concentrate for formulatinglubricating compositions comprising from about 20% to about 90% byweight of a normally liquid, substantially inert, organicsolvent/diluent and from about 80% to about 10% by weight of thepolyamine of claim
 1. 6. An additive concentrate for formulatinglubricating compositions comprising from about 20% to about 90% byweight of a normally liquid, substantially inert, organicsolvent/diluent and from about 80% to about 10% by weight of thepolyamine of claim
 2. 7. A process comprising reacting a mixturecomprising(A) at least one compound represented by the formula:##STR27## wherein each R is independently hydrogen or a hydrocarbyl, Yrepresents S, N, or O; A and X each independently represent an alkylenegroup; n is 0 or 1 dependent upon m and q, where q is 0 or 1, m is 2 or3; with (B) at least one polyamine represented by the formula: ##STR28##wherein each R is hydrogen or a hydrocarbyl group, each R' isindependently hydrogen, alkyl, or NH₂ R"(NR")_(y) where each R" isindependently an alkylene group of 1 to about 10 carbon atoms and y is anumber in the range of from 1 to about 6, each Z is independently aheterocyclic ring containing at least on nitrogen atom and x is a numberint eh range of from 1 to about 10 in the presence of (C) an acidcatalyst at an elevated temperature.
 8. The process of claim 7 whereinreactant (A) is a polyhydric alcohol of formula (II) having 3 hydroxygroups or an amino alcohol of formula (II) having 2 or 3 hydroxy groupsandreactant (B) is a heterocyclic polyamine of formula (III) having atleast 2 primary nitrogen groups wherein Z is a 5- or 6-memberedheterocyclic ring.
 9. The process of claim 7 whereinreactant (A) isselected from the group consisting of glycerol, trimethylolethane,trimethylolpropane, diethanolamine and tris(hydroxymethyl)aminomethane;and reactant (B) is selected from the group consisting of piperazines,pyridines, morpholines, n-aminoalkyl morpholines, pyrrolidines andethylene polyamine bottoms comprising cyclic condensation products andmixtures thereof.
 10. The process of claim 9 wherein reactant (A) istris(hydroxymethyl)aminomethane.
 11. The process of claim 9 whereinreactant (A) is diethanolamine.
 12. The process of claim 7 whereinpolyamine reactant B is an ethylene polyamine bottoms containing lessthan about 2% by weight total diethylenetriamine or triethylenetetramineand containing cyclic condensation products.
 13. The process of claim 12wherein reactant A is tris(hydroxymethyl)aminomethane.
 14. A productproduced according to the process of claim
 7. 15. A product producedaccording to the process of claim
 10. 16. A product produced accordingto the process of claim
 13. 17. A lubricating composition comprising amajor amount of an oil of lubricating viscosity and a minor amount ofthe product according to claim
 16. 18. An additive concentrate forformulating lubricating compositions comprising from about 20% to about90% by weight of a normally liquid, substantially inert, organicsolvent/diluent and from about 80% to about 10% by weight of thepolyamine of claim 16.